Tobacco product



United States Patent 3,306,303 TOBACCO PRODUCT Abraham Bavley, Bon Air, and James Douglas Grossmau, Richmond, Va., assignors to Philip Morris Incorporated, New York, N.Y., a corporation of Virginia No Drawing. Filed May 19, 1964, Ser. No. 368,710 7 Claims. (Cl. 131 17) This invention relates to an improved tobacco product containing a mixture of pyrolysis products. More particularly, the invention relates to improved reconstituted tobacco products containing in the tobacco itself, in the wrapper or in the filt er, a mixture of pyrolysis products.

Reconstituted tobacco has been made by a number of different methods in recent years in an eifort to utilize tobacco parts which had formerly been regarded as waste materials. Such methods have resulted in smoking products made from tobacco fines and from ground tobacco stems, as well as from the tobacco leaves. However, smoking products which have been made from reconstituted tobacco which has been produced from tobacco fines and/ or tobacco stems have been found to be generally less desirable than products made from the tobacco leaves. In general, the side-stream smoke from reconstituted tobacco products has been found to have a less desirable odor and the main-stream smoke has been found to be less pleasant and less mild than that which results from the smoking of conventional leaf-containing tobacco products. Furthermore, such reconstituted tobacco products have generally been found to lack some of the characteristic smoke flavors of leaf tobacco.

In our co-peuding application Serial No. 246,324, which was filed on December 21, 1962, now Patent No. 3,139,- 888, we haveset forth a class of olyisoprenoid alcohols having from 3 to 9 isoprenoid groups, of which solanesol is representative, as additives for tobacco and, particularly, as additives for reconstituted tobacco. We have described, in said application, how such polyisoprenoid alcohols, when incorporated in tobacco, improve the qualities of the tobacco. However, materials such as solanesol and the other polyisoprenoid alcohols containing from 3 to 9 isoprenoid groups have been found to be difficult to obtain. 7

Such materials are usually obtained by either a time-consuming and expensive separation process from materials in which they naturally occur or by chemical synthesis, which is also a time-consuming and expensive procedure. In addition, polyisoprenoid groups containing from 3 to 9 isoprenoid groups do not improve thequalities of tobacco smoke when they are incorporated in a tobacco smoke filter.

Polyisoprenoid alcohols such as geraniol, while more easily obtained, have not been found to be completely satisfactory when incorporated by themselves in tobacco. For example, geraniol cannot be employed to provide mildness in the main-stream smoke since it imparts a very objectionable odor to the smoke when employed in more than minute amounts.

We have unexpectedly discovered that the proper combination of a terpene hydrocarbon (which will, for convenience, also be referred to herein as a. terpene) and a terpene containing a functional oxygen group (which, for convenience, will hereinafter be referred to as an oxygenated terpenoid) can be pyrolyzed to produce a pyrolysis product which can be directly incorporated in tobacco or 3,306,303 Patented Feb. 28, 1967 which, even nore unexpectedly, can-be incorporated in the filter of a tobacco product and which results in a tobacco product which, when smoked, provides outstanding main-stream mildness, reduced side-stream odor and a desirable flavor and aroma.

In accordance with the present invention, a tobacco product, and particularly a product in which the major portion of the tobacco comprises tobacco stems or fines, is greatly improved by the addition thereto .of the product obtained by pyrolyzing a mixture comprising a terpene and an oxygenated terpenoid. Such a pyrolysis product may be incorporated directly in the tobacco or may be applied to the wrapper for the tobacco .or'may be incorporated in a filter to be employed in conjunction with the tobacco. Upon the smoking of such a tobacco product, said pyrolysis product provides a reduction of sidestream odors, a milder main-stream smoke and imparts a desirable flavor note to the tobaccosmoke.

The terpene may be defined as a hydrocarbon of the general formula C H wherein n is an integer-having a value of from 7 to 10, inclusive. p

Theterpenemay be monocyclic, for example a member of the cymene group, an isomer of menthane, dlimonene or menthene. Illustrative of the structure of these materials is menthane, which has the formula C H and the structure:

I orn-on orn and d-limonene, which has the formulaC I-I and has the structure: t i

The terpene may be bicyclic, for example carene, camphene, bornylene, fenchene, alphaand beta-pinene, sabinene and thujene. Illustrative of the formula of these materials are: t

Cam-phone (C H which has the structure:

OH 11 0 I C=CH2 -CHa C CH:

3 Fenchene (C H (H1 0 Ha C H H CH HG CH l \C/ C HG CH3 OH; HO OH: CH:

C H: /C\

HaC C H;

alpha-[enchene gamnm-iencl1ene II C\ I'IIC C C C H:

HaC C H:

beta-fenchene Pinene (C H (IJHQ (3H2 H Ho on I 1ncc cm rno o-om I 2C\ /CH2 H2C\ /CH1 0 l H H ulpha-pinene beta-pinene The terpenes may also include acyclic t'erpenes, for example the aliphatic terpenes. These are illustrated by myrcene (C H which has the structure:

ClHa C Other monocyclic oxygenated terpenoids include:

gamma-terpineol The oxygenated terpenoids may also be bicyclic materials may be illustrated by the structures:

Carnphor (C H O):

The oxygenated terpenoid may also be an acyclic material, such as linalool, gcraniol, nerol, citral and citronellol.

Linalool:

The structural formulas for menthone, dihydrocarvone and piperitone are given below:

Menthone:

Dihydrocarvone Pip eritone The oxygenated terpenoid may also be a terpene alde- U hyde, for example citral 11 0 and citronella] 1o 1s Structural formulas for citral and citronellal are given below-2 The relative proportions of tenpene to oxygenated terpenoid may be between about 120.005 and about 19:1, respectively.

The terpene and the oxygenated terpenoid may also be used in combination with a sequiterpene, an oxygenated sesquiterpene or a mixture of the same, i.e., a mixture of two or more of these materials.

Sesquiterpene hydrocarbons (also referred to herein as sesquiterpenes) which may be employed in accordance with the present invention may be represented by the formula C H and include cadinene, cannibene, caryophyllene, cedrene, clovene, santalene, selinene and zingi berene. Illustrative of the structure of these materials is the bicyclic sesquiterpene, selinene (C H which has the following structural formula:

CH3 CH5 CH2 Oxygenated sesquiterpenes which may be employed in accordance with the present invention may include alcohols, aldehydes and ketones and may be represented OH CH3 H C Ha elemol The oxygenated sesquiterpenes may also be bior tricyclic materials, such as santalol, which may be represented by the formula C I-I 0 and the structures:

CIHs (13H; 0 O

HO OH HG CH3 1 R-CCH3 I ll R-CCHa I HzC OH; HO I OH;

alpha-santalol beta-santalol wherein R is CH CH CH=CCH CH OH and tricyclic materials, such as ce'drol (C I-I 0).

The oxygenated sesquiterpenes may also be straight chain C isoprenoid alcohols such as farnesol (C H O) which has the structure:

The esters, and particularly the lower alkyl esters of the sesquiterpene alcohols, may also be employed and are equivalent to said alcohols.

The relative proportion of sesquiterpenes to the total amount of terpenes and oxygenated terpenoids may be between about 0.5 to 5 parts by weight of the sesquiterpenes per parts of combined terpenes and oxygenated terpenoids which are employed.

In accordance with the present invention, the mixture of terpene and oxygenated terpenoid, which may also include sesquiterpenes, is heated in a pyrolysis zone which is maintained in an inert atmosphere, for example a nitrogen atmosphere, at a temperature of from about 400 C. to about 600 C. The heating is continued within that range for a period of from about one minute to about 24 hours. This operation, which may be called a pyrolysis operation, may be conducted in an oven or other suitable chamber or zone wherein the temperatures can be maintained Within the desired limits and wherein an inert atmosphere can be maintained. The pressure within this pyrolysis zone may vary between about 7 and 50 p.s.i.a. but is preferably about atmospheric pressure.

The pyrolysis products, which are break-down products of the mixture sent to the pyrolysis zone, may be collected by means of a trap, for example, a zone cooled by Dry Ice and acetone or may be passed through any suitable zone wherein the pyrolysis products are condensed. The pyrolysis products could also be recovered by scrubbing with 'Water or an organic solvent or by passing them through Water or an organic solvent.

The collected pyrolysis products, which may be by themselves or may be dissolved or admixed with an organic solvent and/or water, may then be added to the tobacco to be treated by the following methods:

(1) They may be sprayed, painted, injected or otherwise applied to the tobacco or the filter, while in substantially undiluted form.

(2) They may be dissolved in a solvent to form a solution or may be admixed with an organic material or water to form a suspension or an emulsion and applied to the tobacco or the filter by spraying, painting and the like. When employed together with a solvent or suspending agent, they may be employed in the ratio of from about 0.5 to about 50 parts per 100 parts of solvent or suspending agent.

The amount of pyrolysis product which should be employed, in accordance with the present invention, :may vary between about 0.025 part to 5.0 parts by weight per 100 parts of tobacco and is preferably from about 0.05 to 1.0 part by weight per 100 part of tobacco.

The invention can be illustrated by the following examples:

Example 1 A mixture of 70.0% d-limonene, 30.0% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geranoil) was passed at the rate of 20 drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was 20 grams and the pyrolysis was contained for approximately 2 hours. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromotography. The gas chromatographic analysis indicated that 35 components were present in the mixture and that, in the mixture, 30.28% was d-limonene, 8.7% was citronellol, 0.58% was nerol and 1.32% was geraniol.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in 100 grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-1imonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarettes was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 2 A mixture of 90% d-limonene, commercial geraniol (a mixture consisting of 36.5% citronellol,

which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was 20 grams and the pyrolysis was continued for approximately 2 hours. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 31 components were present in the mixture and that, in the mixture, 35.5% was d-limonene, 4.15% was citronellol, 0.39% was nerol and 0.8% was geraniol.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in 100 grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 3 A mixture of d-limonene, 5% commercial geraniol (a mixture consisting of 36.5% citronellol,

2.13% nerol and 61.37% geraniol), and 5% farnesol was passed at the rate of 20 drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was 20 grams and the pyrolysis was continued for approximately 2 hours. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 35 components were present in the mixture and that, in the mixture, 44.2% was d-limonene, 2.0% was citronellol, 0.2% was nerol and 0.45% was geraniol.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 4 A mixture of 92.5% d-lirnonene, 2.5% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geraniol), and 5% farnesol was passed at the rate of drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was grams and the pyrolysis was continued for approximately 150 minutes. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that components were present in the mixture and that, in the mixture, 31.2% was d-limonene.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in 100 grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial gerani-ol in the same concentration as the pyrolysis product and it was found that the genaniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and mainstream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and the cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemonlike flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 5 A mixture of 90.0% d-limonene, 2.5% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geraniol), and 7.5% farnesol was passed at the rate of 20 drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyr-olyze the mixture. The amount of the mixture employed was 15 grams and the pyrolysis was continued for approximately minutes. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 32 components were present in the mixture and that, in the mixture, 36.7% was d-limonene.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. Gne gram of the total pyrolysis product described above was dissolved in grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and. adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the gerani-ol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and mainstream smoke.

For additional comparison, cigaettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 6 A mixture of 87.5% d-limonene, 5.0% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geraniol), 5% farnesol and 2.5% cedrol was passed at the rate of 20 drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was 20 grams and the pyrolysis was continued for approximately 2 hours.

The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 35 components were present in the mixture.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in 100 grams of ethanol and sprayed on one 100 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 7 A mixture of 87.5% d-limonene, 5.0% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geraniol), farnesol and 2.5% santalol, was passed at the rate of drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was grams and the pyrolysis was continued for approximately minutes. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 35 components were present in the mixture.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in 100 grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged 12 that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type Were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemonlike flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filter. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 8 A mixture of 88.75% d-limonene, 5.0% commercial geraniol (a mixture consisting of 36.5% citronellol, 2.13% nerol and 61.37% geraniol), 5% farnesol and 1.25% santalol, was passed at the rate of 20 drops per minute through a tube containing porcelain chips and a stream of nitrogen gas was passed through the tube, while the tube was heated in a furnace which was maintained at a temperature of about 500 C. to pyrolyze the mixture. The amount of the mixture employed was 20 grams and the pyrolysis Was continued for approximately 2 hours. The pyrolysis products were collected in a trap which was cooled by a Dry Ice acetone mixture. The pyrolysis products were analyzed by gas chromatography. The gas chromatographic analysis indicated that 35 components were present in the mixture.

Reconstituted tobacco sheet was shredded and divided into two 1000 gram portions. One gram of the total pyrolysis product described above was dissolved in grams of ethanol and sprayed on one 1000 gram portion and the resulting mixture was employed to prepare cigarettes. The cigarettes were prepared without a filter and had a length of 8 cm. Control cigarettes were made identical in size and construction to the test cigarettes from the other 1000 gram batch portion of shredded tobacco except that they were not sprayed.

A smoking panel of 12 judges evaluated both types of cigarettes and adjudged the side-stream smoke of the experimental cigarettes to be a pleasing citrus type odor and adjudged the main-stream smoke to have a note similar to that of lemon oil. The panel also adjudged that the harshness of the smoke was reduced over that which existed in the control cigarettes.

For comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of commercial geraniol in the same concentration as the pyrolysis product and it was found that the geraniol treated cigarettes gave an undesirable floral note, had a harsher smoke and resulted in less desirable side-stream smoke and main-stream smoke.

For additional comparison, cigarettes of the same type were prepared by spraying them with an ethanol solution of d-limonene in the same concentration as the pyrolysis product and cigarettes of the same type were fitted with filter plugs which had been sprayed with d-limonene to give from 0.1 to 1.0% d-limonene per cigarette. It was found that the smoke from all such cigarettes gave lemon-like flavor which was unlike the flavors which resulted when the pyrolysis mixture of the present invention was added to tobacco filler. In addition, the smoke of the d-limonene treated cigarette was found to be harsher and the side-stream and main-stream smokes were found to be less desirable.

Example 9 A starting material consisting of commercial geraniol, 5% farnesol, 87.5% d-limonene, and 2.5% santalyl acetate was pyrolyzed as described in Example 1 at 500 C. for 2 hours. The resulting pyrolyzate mixture was shown by gas chromatography to have 38 components. This mixture was repyrolyzed in the same manner at 500 C. for 90 minutes and again analyzed by gas chromatography. Forty-one components were present. The second resulting pyrolyzate mixture was further pyrolyzed at 550 C. for 85 minutes and gas chromatographed. Forty components were present among which the following compounds were identified by gas chromatography: 2-methyl butene, isoprene, pyronenes, dimethyl-vinyl-cyclohexene, A-l-menthene, dlimonene, para-cymene, citronellol, nerol, and gerauiol.

The final pyrolyzate mixture was applied to the carbon portion of a dual-plug cigarette filter by injecting the mixture into the plug with a syringe. Varying levels (0.01% to 0.2% of the basic weight of the attached cigarette filler rod) were injected. The cigarettes were smoked against a control cigarette which had no additive in the filter or filler.

It was found that the preferred range of application of the pyrolyzate mixture was 0.5-1.0 microliter.

The cigarettes, according to evaluation by a descriptive panel of seven judges, found that the smoke had a fresh, slightly piney odor and no taste characteristic of d-limonene. The treated cigarette was preferred over the control for its aroma and for its mild taste.

Example The same combination of materials given in Example 9 for the starting mixture was pyrolyzed as described in Example 1 at 550 C. for 115 minutes. The resulting pyrolyzate mixture was shown by gas chromatography to have 37 components. This mixture was repyrolyzed in the same manner at 550 C. for 95 minutes. Gas chromatography of the resulting pyrolyzate mixture showed that 40 components were present among which the following were identified: Z-methyl butene, isoprene, pyronenes, dimethyl-vinyl-cyclohexene, A-l-menthene, dlimonene, para-cymene, and citronellol. Nerol and geraniol were not present as they had been in the pyrolyzate mixture described in Example 9.

The final pyrolyzate mixture was applied to the carbon portion of a dual-plug cigarette filter by injecting the mixture into the plug with a syringe. Varying levels (0.01% to 0.2% of the basic weight of the attached cigarette filler rod) were injected. The cigarettes were smoked by six judges against a control cigarette which had no pyrolyzate additives in the filter or filler. All of the judges preferred the test cigarette over the control. The test cigarette had a slight limonene note, and the characteristic carbon and paper tastes were reduced.

Example 11 The same starting materials used in Example 9 were pyrolyzed as described in Example 1 at 550 C. for 115 minutes.

The pyrolyzate was injected by syringe into the carbon portion of a dual-plug filter cigarette.

Gas chromatographic analysis of the pyrolyzate showed that 37 components were present.

Subjective evaluation of the smoke from the cigarette (smoked against an untreated control) showed that its aroma was more desirable than that of the control and that it was less harsh.

Unless otherwise specified, all parts and percentages, as used in this specification, are by weight.

We claim:

1. A tobacco product containing tobacco and from 0.025% to 5.0% by weight, based on the tobacco, of the product obtained by the pyrolysis of a mixture comprising from 1 to 30% by weight of anoxygenated terpenoid and from to 99% of a terpene, wherein said pyrolysis is conducted in an inert atmosphere at a temperature of from about 400 C. to about 600 C. for a period of time of from about 1 minute to about 24 hours, to produce a pyrolysis product, said pyrolysis product, when incorporated in said tobacco product and smoked, providing improved main-stream mildness, reduced side-stream odor and desirable flavor and aroma.

2. A tobacco product containing tobacco and from 0.5 to 1.0% by weight, based on the tobacco, of the product obtained by the pyrolysis of a mixture comprising from 1 to 5% by weight of an oxygenated terpenoid and from to 99% of .a terpene, wherein said pyrolysis is conducted in an inert atmosphere at a temperature of from about 400 C. to about 600 C. for a period of time of from about 1 minute to about 24 hours, to produce a pyrolysis product, said pyrolysis product, when incorporated in said tobacco product and smoked, providing improved main-stream mildness, reduced side-stream odor and desirable flavor and aroma.

3. A tobacco product containing tobacco and from 0.025 to 5% by weight, based on the tobacco, of the product obtained by the pyrolysis of a mixture comprising 70 to 99%, by weight of a terpene, from 0.5 to 29.5% by Weight of an oxygenated terpenoid and from 0.5 to 29.5 of a member selected from the group consisting of sesquiterpenes, oxygenated sesquiterpenes and mixtures of the same, wherein said pyrolysis is conducted in an inert atmosphere at a temperature of from about 400 C. to about 600 C. for a period of time of from about 1 minute to about 24 hours, to produce a pyrolysis product, said pyrolysis product, when incorporated in said tobacco product and smoked, providing improved main stream mildness, reduced side-stream odor and desirable flavor and aroma.

4. The tobacco product of claim 1 wherein the terpene is d-limonene.

5. The tobacco product of claim 1 wherein the oxygenated terpenoid is geraniol.

6. The tobacco product of claim 1 wherein the oxygenated terpenoid is geraniol and the terpene is d-limonene.

7. The tobacco product of claim 1 wherein the oxygenated terpenoid is a mixture of citronellol, nerol and geraniol and the terpene is d-limonene. 

1. A TOBACCO PRODUCT CONTAINING TOBACCO AND FROM 0.025% TO 5.0% BY WEIGHT, BASED ON THE TOBACCO, OF THE PRODUCT OBTAINED BY THE PYROLYSIS OF A MIXTURE COMPRISING FROM 1 TO 30% BY WEIGHT OF AN OXYGENATED TERPENOID AND FROM 70 TO 99% OF A TERPENE, WHEREIN SAID PYROLYSIS IS CONDUCTED IN AN INERT ATMOSPHERE AT A TEMPERATURE OF FROM ABOUT 400*C. TO ABOUT 600*C. FOR A PERIOD OF TIME OF FROM ABOUT 1 MINUTE TO ABOUT 24 HOURS, TO PRODUCE A PYROLYSIS PRODUCT, SAID PYROLYISS PRODUCT, WHEN INCORPORATED IN SAID TOBACCO PRODUCT AND SMOKED, PROVIDING IMPROVED MAIN-STREAM MILDNESS, REDUCED SIDE-STREAM ODOR AND DESIRABLE FLAVOR AND AROMA. 